Pyrazolyl biphenyl carboxamides and the use thereof for controlling undesirable microorganisms

ABSTRACT

Novel pyrazolylbiphenylcarboxamides of the formula (I)  
                 
in which 
 
R 1 , R 2 , X, m, Y and n are each as defined in the description, 
a plurality of processes for preparing these substances and their use for controlling undesirable microorganisms, and also novel intermediates and their preparation.

The present invention relates to novel pyrazolylbiphenylcarboxamides, toa plurality of processes for their preparation and to their use forcontrolling undesirable microorganisms.

It is already known that numerous carboxanilides have fungicidalproperties (compare WO 93/11 117, EP-A 0 545 099, EP-A 0 589 301, WO99/09013, DE 198 40 322). Thus,N-(2-cyclohexyl)-1,3-dimethyl-5-fluoropyrazole-4-carboxanilide,N-(2-phenyl)-1,3-dimethyl-pyrazole-4-carboxanilide andN-2[2-(2-fluoro-phenyl)]-1,3-dimethyl-pyrazole-4-carboxanilide can beemployed for controlling fungi. The activity of these substances isgood; however, in some cases it is unsatisfactory at low applicationrates.

This invention, accordingly, provides novelpyrazolylbiphenylcarboxamides of the formula (I)

in which

-   R¹ represents hydrogen, C₁-C₆-alkyl, C₁-C₆-halogenoalkyl, benzyl or    pyridylmethyl,-   R² represents hydrogen or C₁-C₆-alkyl,-   X represents halogen, nitro, cyano, hydroxyl, carboxyl, C₁-C₈-alkyl,    C₁-C₆-halogenoalkyl having 1 to 5 halogen atoms, C₁-C₈-alkoxy,    C₁-C₆-halogenoalkoxy having 1 to 5 halogen atoms, C₁-C₈-alkylthio,    C₁-C₆-halogenoalkylthio having 1 to 5 halogen atoms,    C₂-C₈-alkenyloxy, C₂-C₈-alkinyloxy, C₃-C₈-cycloalkyl,    C₁-C₈-alkoxycarbonyl or represents —C(R²)═N—OR¹,-   m represents integers from 0 to 3, where X represents identical or    different radicals if m represents 2 or 3,-   Y represents halogen, nitro, cyano, hydroxyl, carboxyl, C₁-C₈-alkyl,    C₁-C₆-halogenoalkyl having 1 to 5 halogen atoms, C₁-C₈-alkoxy,    C₁-C₆-halogenoalkoxy having 1 to 5 halogen atoms, C₁-C₈-alkylthio,    C₁-C₆-halogenoalkylthio having 1 to 5 halogen atoms,    C₂-C₈-alkenyloxy, C₂-C₈-alkinyloxy, C₃-C₈-cycloalkyl,    C₁-C₈-alkoxycarbonyl or C₁-C₆-alkoximino-C₁-C₆-alkyl and-   n represents integers from 0 to 4, where Y represents identical or    different radicals if n represents 2, 3 or 4.

Furthermore, it has been found that pyrazolylbiphenylcarboxamides of theformula (I) are obtained when

-   a) carboxylic acid derivatives of the formula (II)    -   in which    -   G represents halogen, hydroxyl or C₁-C₆-alkoxy,    -   are reacted with aniline derivatives of the formula (III)    -   in which    -   R¹, R², X, m, Y and n are each as defined above,    -   if appropriate in the presence of a catalyst, if appropriate in        the presence of an acid binder and if appropriate in the        presence of a diluent,        or-   b) carboxamide derivatives of the formula (IV)    -   in which    -   X and m are each as defined above,    -   are reacted with boronic acid derivatives of the formula (V)    -   in which    -   R¹, R², Y and n are each as defined above and    -   G¹ and G² each represent hydrogen or together represent        tetramethylethylene,    -   if appropriate in the presence of a catalyst, if appropriate in        the presence of an acid binder and if appropriate in the        presence of a diluent,        or-   c) carboxamide-boronic acid derivatives of the formula (VI)    -   in which    -   X and m are each as defined above and    -   G¹ and G² each represent hydrogen or together represent        tetramethylethylene,    -   are reacted with phenyloxime derivatives of the formula (VII)    -   in which    -   R¹, R²,Y and n are each as defined above,    -   if appropriate in the presence of a catalyst, if appropriate in        the presence of an acid binder and if appropriate in the        presence of a diluent,        or-   d) biphenylacyl derivatives of the formula (VII)    -   in which    -   R², X, m, Y and n are each as defined above and    -   are reacted with alkoxamines of the formula (IX)        R¹—O—NH₂×HCl  (IX)    -   in which R¹ is as defined above,    -   if appropriate in the presence of an acid binder and if        appropriate in the presence of a diluent,        or-   e) hydroxylamine derivatives of the formula (I-a)    -   in which    -   R², X, m, Y and n are each as defined above,    -   are reacted with compounds of the formula (X)        R³-E  (X)    -   in which    -   R³ represents C₁-C₆-alkyl and    -   E represents chlorine, bromine, iodine, methanesulphonyl or        p-toluenesulphonyl,    -   or    -   R³ and E together represent di-C₁-C₆-alkyl sulphate,    -   if appropriate in the presence of an acid binder and if        appropriate in the presence of a diluent,        or-   f) carboxamide derivatives of the formula (IV)    -   in which    -   X and m are each as defined above,    -   are reacted with phenyloxime derivatives of the formula (VII)    -   in which    -   R¹, R², Y and n are each as defined above,    -   in the presence of a palladium or platinum catalyst and in the        presence of        4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis-1,3,2-dioxaborolane, if        appropriate in the presence of an acid binder and if appropriate        in the presence of a diluent.

Finally, it has been found that the novel pyrazolylbiphenylcarboxamidesof the formula (I) have very good microbicidal properties and can beused for controlling undesirable microorganisms both in crop protectionand in the protection of materials.

Surprisingly, the pyrazolylbiphenylcarboxamides of the formula (I)according to the invention have considerably better fungicidal activitythan the active prior-art compounds of the most similar constitution andthe same direction of action.

The formula (I) provides a general definition of thepyrazolylbiphenylcarboxamides according to the invention.

-   R¹ preferably represents hydrogen, C₁-C₄-alkyl, C₁-C₂-halogenoalkyl    having 1 to 5 fluorine, chlorine and/or bromine atoms, benzyl or    pyridylmethyl.

R² preferably represents hydrogen or C₁-C₄-alkyl.

X preferably represents fluorine, chlorine, bromine, nitro, cyano,hydroxyl, carboxyl, C₁-C₆-alkyl, C₁-C₂-halogenoalkyl having 1 to 5fluorine, chlorine and/or bromine atoms, C₁-C₆-alkoxy,C₁-C₂-halogenoalkoxy having 1 to 5 fluorine, chlorine and/or bromineatoms, C₁-C₆-alkylthio, C₁-C₂-halogenoalkylthio having 1 to 5 fluorine,chlorine and/or bromine atoms, C₂-C₆-alkenyloxy, C₂-C₆-alkinyloxy,C₃-C₇-cycloalkyl, C₁-C₄-alkoxycarbonyl or represents C(R²)═N-OR¹.

-   m preferably represents integers from 0 to 3, where X represents    identical or different radicals if m represents 2 or 3.-   Y preferably represents fluorine, chlorine, bromine, nitro, cyano,    hydroxyl, carboxyl, C₁-C₆-alkyl, C₁-C₂-halogenoalkyl having 1 to 5    fluorine, chlorine and/or bromine atoms, C₁-C₆-alkoxy,    C₁-C₂-halogenoalkoxy having 1 to 5 fluorine, chlorine and/or bromine    atoms, C₁-C₆-alkylthio, C₁-C₂-halogenoalkylthio having 1 to 5    fluorine, chlorine and/or bromine atoms, C₂-C₆-alkenyloxy,    C₂-C₆-alkinyloxy, C₃-C₇-cycloalkyl, C₁-C₄-alkoxycarbonyl or    C₁-C₄-alkoximino-C₁-C₄-alkyl.-   n preferably represents integers from 0 to 3, where Y represents    identical or different radicals if n represents 2 or 3.-   R¹ particularly preferably represents hydrogen, methyl, ethyl,    n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl,    2-chloroethyl, benzyl, 2-pyridylmethyl, 3-pyridylmethyl or    4-pyridylmethyl.-   R² particularly preferably represents hydrogen, methyl, ethyl,    n-propyl, i-propyl or n-butyl.-   X particularly preferably represents fluorine, chlorine, bromine,    nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl,    isopropyl, n-butyl, sec-butyl, i-butyl, tert-butyl, trichloromethyl,    trifluoromethyl, difluoromethyl, difluoro-chloromethyl, methoxy,    ethoxy, difluoromethoxy, trifluoromethoxy, methylthio,    trifluoromethylthio, difluorochloromethylthio, allyloxy,    propargyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl,    methoxycarbonyl, ethoxycarbonyl or represents —C(R²)═N-OR¹.-   m particularly preferably represents integers from 0 to 2, where X    represents identical or different radicals if m represents 2.-   Y particularly preferably represents fluorine, chlorine, bromine,    nitro, cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl,    isopropyl, n-butyl, sec-butyl, i-butyl, tert-butyl, trichloromethyl,    trifluoromethyl, difluoromethyl, difluoro-chloromethyl, methoxy,    ethoxy, difluoromethoxy, trifluoromethoxy, methylthio,    trifluoromethylthio, difluorochloromethylthio, allyloxy,    propargyloxy, cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl,    methoxycarbonyl, ethoxycarbonyl or methoximinomethyl.-   n particularly preferably represents integers from 0 to 2, where Y    represents identical or different radicals if n represents 2.

Preference is also given to compounds of the formula (I-b)

in whichR¹, R², X, m, Y and n are each as defined above.

Particular preference is given to compounds of the formula (I-b) inwhich R¹, R², X, m, Y and n have the meanings given above as beingpreferred or as being particularly preferred.

Preference is furthermore given to compounds of the formula (I-c)

in whichR¹, R², X, m, Y and n are each as defined above.

Particular preference is given to compounds of the formula (I-c) inwhich R¹, R², X, m, Y and n have the meanings given above as beingpreferred or as being particularly preferred.

Preference is furthermore given to compounds of the formula (I-d)

in whichR¹, R², X, m, Y and n are each as defined above.

Particular preference is given to compounds of the formula (I-d) inwhich R¹, R², X, m, Y and n have the meanings given above as beingpreferred or as being particularly preferred.

Preference or particular preference is given to compounds which carrythe stibstituents mentioned under preferred or particularly preferred.

Saturated or unsaturated hydrocarbon radicals, such as alkyl or alkenyl,can in each case be straight-chain or branched as far as this ispossible, including in combination with hetero atoms, such as, forexample, in alkoxy.

Optionally substituted radicals can be mono- or polysubstituted, wherein the case of polysubstitution the substituents can be identical ordifferent. A plurality of radicals having the same indices, such as, forexample, m radicals X for m>1, can be identical or different.

Halogen-substituted radicals, such as, for example, halogenoalkyl, aremono- or polyhalogenated. In the case of polyhalogenation, the halogenatoms can be identical or different. Here, halogen represents fluorine,chlorine, bromine and iodine, in particular fluorine, chlorine andbromine.

However, the abovementioned general or preferred radical definitions orillustrations can also be combined with one another as desired, i.e.including combinations between the respective ranges and preferredranges. The definitions apply to the end products and, correspondingly,to the precursors and intermediates.

The abovementioned definitions can be combined with one another asdesired. Moreover, individual definitions may not apply.

Using 1,3-dimethyl-5-fluoropyrazole-4-carbonyl chloride and2-(4-methoximino-methyl-phenyl)aniline as starting materials, the courseof the process (a) according to the invention can be illustrated by theequation below.

Using 2′-bromo-1,3-dimethyl-5-fluoropyrazol-4-carboxanilide and(4-methoximino-methyl)-phenylboronic acid as starting materials and acatalyst, the course of the process (b) according to the invention canbe illustrated by the equation below.

Using 2-[(1,3-dimethyl-5-fluoropyrazol-4-yl)carbonylamino]phenyl-boronicacid and 1-bromo-2-methoximinomethyl-benzene as starting materials and acatalyst, the course of the process (c) according to the invention canbe illustrated by the equation below.

Using2′-(4-acetyl-phenyl)-4′-fluoro-1,3-dimethyl-5-fluoropyrazole-4-carboxanilideand methoxamine hydrochloride as starting materials, the course of theprocess (d) according to the invention can be illustrated by theequation below.

Using2′-(4-hydroximinoethyl)-phenyl-1,3-dimethyl-5-fluoropyrazole-4-carboxanilideand methyl bromide as starting materials, the course of the process (e)according to the invention can be illustrated by the equation below.

Using 2′-bromo-1,3-dimethyl-5-fluoropyrazole-4-carboxanilide and1-bromo-4-methoximinomethyl-benzene as starting materials and a catalystand 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis-1,3,2-dioxaborolane, thecourse of the process (f) according to the invention can be illustratedby the equation below.

Illustration of the Processes and Intermediates

The formula (II) provides a general definition of the carboxylic acidderivatives required as starting materials for carrying out the process(a) according to the invention. In this formula, G preferably representschlorine, bromine, hydroxyl, methoxy or ethoxy, particularly preferablychlorine, hydroxyl or methoxy.

The carboxylic acid derivatives of the formula (II) are known or can beprepared by known processes (cf. WO 93/11 117, EP-A 0 545 099, EP-A 0589 301 and EP-A 0 589 313).

The formula (III) provides a general definition of the anilinederivatives required as reaction components for carrying out the process(a) according to the invention. In this formula, R¹, R², X, m, Y and neach preferably have those meanings which have already been mentioned inconnection with the description of the substances of the formula (I)according to the invention as being preferred or being particularlypreferred for these radicals or indices.

The aniline derivatives of the formula (III) are novel. Some of them canbe prepared by known methods (cf. EP-A 0 545 099 and EP-A 0 589 301).

The aniline derivatives of the formula (III) are furthermore obtained by

-   g) reacting 2-halogenoaniline derivatives of the general formula    (XI)    -   in which    -   X and m are each as defined above and    -   Hal represents halogen,    -   with boronic acid derivatives of the formula (V)    -   in which R¹, R², Y, n, G¹ and G² are each as defined above,    -   if appropriate in the presence of an acid binder, and if        appropriate in the presence of an inert organic diluent, and if        appropriate in the presence of a catalyst,    -   or-   h) by reacting anilineboronic acids of the formula (XII)    -   in which    -   X, m, G¹ and G² are each as defined above    -   with phenyloxime derivatives of the formula (VII)    -   in which R¹, R², Y and n are each as defined above,    -   if appropriate in the presence of an acid binder, and if        appropriate in the presence of an inert organic diluent, and if        appropriate in the presence of a catalyst.

The formula (XI) provides a general definition of the 2-halogenoanilinederivatives required as reaction components for carrying out the process(g) according to the invention. In this formula, X and m each preferablyhave those meanings which have already been mentioned in connection withthe description of the substances of the formula (I) according to theinvention as being preferred or as being particularly preferred forthese radicals or these indices. Hal preferably represents fluorine,chlorine or bromine, in particular chlorine or bromine.

The 2-halogenoaniline derivatives of the formula (XI) are commerciallyavailable or can be prepared from the corresponding nitro compounds byreduction.

The formula (XII) provides a general definition of the anilineboronicacids required as reaction components for carrying out the process (h)according to the invention. In this formula, X and m each preferablyhave those meanings which have already been mentioned in connection withthe description of the substances of the formula (I) according to theinvention as being preferred or as being particularly preferred forthese radicals or these indices. G¹ and G² preferably each representhydrogen or together represent tetramethylethylene.

The anilineboronic acids of the formula (XII) are commerciallyavailable.

The formula (V) provides a general definition of the carboxamidederivatives required as starting materials for carrying out theprocesses (b) and (f) according to the invention. In this formula, X andm each preferably have those meanings which have already been mentionedin connection with the description of the substances of the formula (I)according to the invention as being preferred or as being particularlypreferred for these radicals.

The carboxamide derivatives of the formula (IV) are known or can beprepared by known processes (cf. WO 91/01311, EP-A 0 371 950).

The formula (V) provides a general definition of the boronic acidderivatives required as reaction components when carrying out theprocess (b) and the process (g) according to the invention. In thisformula, R¹, R², Y and n each preferably have those meanings which havealready been mentioned in connection with the description of thesubstances of the formula (I) according to the invention as beingpreferred or as being particularly preferred for these radicals or theseindices.

The boronic acid derivatives of the fonnula (V) are novel and can beprepared by

-   i) reacting phenylboronic acids of the formula (XIII).    -   in which    -   R¹, Y, n, G¹ and G² are each as defined above,    -   with alkoxamines of the formula (IX)        R¹—O—NH₂×HCl  (IX)    -   in which    -   R¹ is as defined above,    -   if appropriate in the presence of an acid binder, and if        appropriate in the presence of an inert organic diluent, and if        appropriate in the presence of a catalyst.

The formula (XIII) provides a general definition of the phenylboronicacids required as reaction components for carrying out the process (h)according to the invention. In this formula, R², Y and n each preferablyhave those meanings which have already been mentioned in connection withthe description of the substances of the formula (I) according to theinvention as being preferred or as being particularly preferred forthese radicals or these indices. G¹ and G² preferably each representhydrogen or together represent tetramethylethylene.

The phenylboronic acids of the formula (XIII) are commerciallyavailable.

The formula (VI) provides a general definition of thecarboxamide-boronic acid derivatives required as reaction components forcarrying out the process (c) according to the invention. In thisformula, X and m each preferably have those meanings which have alreadybeen mentioned in connection with the description of the substances ofthe formula (I) according to the invention as being preferred or asbeing particularly preferred for these radicals. G¹ and G² preferablyeach represent hydrogen or together represent tetramethylethylene.

The carboxamide-boronic acid derivatives of the formula (VI) are novel.They can be prepared by

-   j) reacting carboxylic acid derivatives of the formula (II)    -   in which    -   G is as defined above,    -   with anilineboronic acids of the formula (XII)    -   in which    -   X, m, G¹ and G² are each as defined above,    -   if appropriate in the presence of an acid binder, and if        appropriate in the presence of an inert organic diluent, and if        appropriate in the presence of a catalyst.

The formula (VII) provides a general definition of the phenyloximederivatives required as reaction components for carrying out theprocesses (c), (f) and (h) according to the invention. In this formulaR¹, R², Y and n each preferably have those meanings which have alreadybeen mentioned in connection with the description of the substances ofthe formula (I) according to the invention as being preferred or asbeing particularly preferred for these radicals.

The phenyloxime derivatives of the formula (VII) are known or can beprepared by known processes (cf. Synth. Commun. 2000, 30, 665-669,Synth. Commun. 1999, 29, 1697-1701).

The formula (VIII) provides a general definition of the biphenylacylderivatives required as starting materials for carrying out the process(d) according to the invention. In this formula, R², X, m, Y and n eachhave those meanings which have already been mentioned in connection withthe description of the substances of the formula (I) according to theinvention as being preferred or as being particularly preferred forthese radicals.

The biphenylacyl derivatives of the formula (VIII) are novel. They canbe prepared by

-   k) reacting carboxylic acid derivatives of the formula (II)    -   in which    -   G is as defined above,    -   with 2-benzaldehyde-aniline derivatives of the formula (XIV)    -   in which    -   R², X, m, Y and n are each as defined above,    -   if appropriate in the presence of an acid binder, and if        appropriate in the presence of an inert organic diluent.

The formula (XIV) provides a general definition of the2-benzaldehyde-aniline derivatives required as reaction components forcarrying out the process (k) according to the invention. In thisformula, R², X, m, Y and n each preferably have those meanings whichhave already been mentioned in connection with the description of thesubstances of the formula (I) according to the invention as beingpreferred or as being particularly preferred for these radicals.

The 2-benzaldehyde-aniline derivatives of the formula (XIV) are novel.They can be prepared by

-   1) reacting aniline derivatives of the formula (XI)    -   in which    -   X and m are each as defined above and    -   Hal represents halogen,    -   with phenylboronic acid derivatives of the formula (XIII)    -   in which    -   R², Y, n, G¹ and G² are each as defined above,    -   if appropriate in the presence of an acid binder, and if        appropriate in the presence of an inert organic diluent.

The formula (IX) provides a general definition of the alkoxarninesrequired as reaction components for carrying out the process (d)according to the invention and the process (i). In this formula, R¹preferably has those meanings which have already been mentioned inconnection with the description of the substances of the formula (I)according to the invention as being preferred or as being particularlypreferred for this radical. Preference is given to using thehydrochlorides mentioned in the description. However, it is alsopossible to use the free alkoxamines for the process according to theinvention.

The alkoxamines of the formula (IX) are commercially available.

The formula (I-a) provides a general definition of the hydroxylaminederivatives required as starting materials for carrying out the process(e) according to the invention. In this formula, R², X, m, Y and n eachpreferably have those meanings which have already been mentioned inconnection with the description of the substances of the formula (I)according to the invention as being preferred or as being particularlypreferred for these radicals.

The hydroxylamine derivatives of the formula (I-a) according to theinvention are novel. They can be prepared by one of the processes (a),(b), (c), (d) or (f) according to the invention described above.

The formula (X) provides a general definition of the compounds requiredas reaction components for carrying out the process (e) according to theinvention. In this formula R³ preferably represents C₁-C₄-alkyl, inparticular methyl, ethyl, n-propyl, i-propyl or n-butyl. E preferablyrepresents chlorine, bromine, iodine, methanesulphonyl orp-toluenesulphonyl. E particularly preferably represents chlorine orbromine.

The compounds of the formula (X) are commercially available.

Suitable acid binders for carrying out the processes (a), (b), (c), (d),(e) and (f) according to the invention are in each case all inorganicand organic bases which are customary for such reactions. Preference isgiven to using alkaline earth metal or alkali metal hydroxides, such assodium hydroxide, calcium hydroxide, potassium hydroxide, or elseammonium hydroxide, alkali metal carbonates, such as sodium carbonate,potassium carbonate, potassium bicarbonate, sodium bicarbonate, alkalimetal or alkaline earth metal acetates, such as sodium acetate,potassium acetate, calcium acetate, and also tertiary amines, such astrimethylamine, triethylamine, tributylamine, N,N-dimethylaniline,pyridine, N-methylpiperidine, N,N-dimethylaminopyridine,diazabicyclooctane (DABCO), diazabicyclononene (DBN) ordiazabicycloundecene (DBU). However, it is also possible to work in theabsence of an additional acid binder or to employ an excess of the aminecomponent, so that it simultaneously acts as acid binder.

Suitable diluents for carrying out the processes (a), (b), (c), (d), (e)and (f) according to the invention are in each case all customary inertorganic solvents. Preference is given to using optionally halogenatedaliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether,hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene,xylene or decalin; chlorobenzene, dichlorobenzene, dichloromethane,chloroform, carbon tetrachloride, dichloroethane or trichloroethane;ethers, such as diethyl ether, diisopropyl ether, methyl t-butyl ether,methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,1,2-diethoxyethane or anisol; nitriles, such as acetonitrile,propionitrile, n- or i-butyronitrile or benzonitrile; amides, such asN,N-dimethylformamide, N,N-dimethylacetamide, N-methylformanilide,N-methylpyrrolidone or hexamethylphosphoric triamide; esters, such asmethyl acetate or ethyl acetate, sulphoxides, such as dimethylsulphoxide, or sulfones, such as sulfolane.

When carrying out the processes (a), (b), (c), (d), (e) and (f)according to the invention, the reaction temperatures can in each casebe varied within a relatively wide range. In general, the processes arecarried out at temperatures between 0° C. and 140° C., preferablybetween 10° C. and 120° C.

The processes (a), (b), (c), (d), (e) and (f) according to the inventionare generally in each case carried out under atmospheric pressure.However, in each case, it is also possible to operate under elevated orreduced pressure.

When carrying out the process (a) according to the invention, in general1 mol or else an excess of the aniline derivative of the formula (III)and from 1 to 3 mol of acid binder are employed per mole of acid halideof the formula (II). However, it is also possible to employ the reactioncomponents in other ratios. Work-up is carried out by customary methods.In general, the reaction mixture is mixed with water and the organicphase is separated off and, after drying, concentrated under reducedpressure. The residue that remains can, if appropriate, be freed bycustomary methods, such as chromatography or recrystallization, from anyimpurities that may be present.

When carrying out the process (b) according to the invention, in general1 mol or else an excess of the boronic acid derivative of the formula(V) and from 1 to 5 mol of acid binder are employed per mole ofcarboxamide of the formula (IV). However, it is also possible to employthe reaction components in other ratios. Work-up is carried out bycustomary methods. In general, the reaction mixture is mixed with waterand the precipitate is separated off and dried. The residue that remainscan, if appropriate, be freed by customary methods, such aschromatography or recrystallization, from any impurities that may bepresent.

When carrying out the process (c) according to the invention, in general1 mol or else an excess of the phenyloxime derivative of the formula(VII) and from 1 to 10 mol of acid binder and from 0.5 to 5 mol percentof a catalyst are employed per mole of carboxamide-boronic acidderivative of the formula (VI). However, it is also possible to employthe reaction components in other ratios. Work-up is carried out bycustomary methods. In general, the reaction mixture is mixed with waterand the precipitate is separated off and dried. The residue that remainscan, if appropriate, be freed by customary methods, such aschromatography or recrystallization, from any impurities that may bepresent.

When carrying out the process (d) according to the invention, in general1 mol or else an excess of the alkoxamine of the formula (IX) and from 1to 5 mol of acid binder are employed per mole of biphenylacyl derivativeof the formula (VIII). However, it is also possible to employ thereaction components in other ratios. Work-up is carried out by customarymethods. In general, the reaction mixture is mixed with water and theprecipitate is separated off, washed with water and diisopropyl etherand then dried. The residue that remains can, if appropriate, be freedby customary methods, such as chromatography or recrystallization, fromany impurities that may be present.

When carrying out the process (e) according to the invention, in general1 mol or else an excess of the reagent of the formula (X) and from 1 to5 mol of acid binder are employed per mole of hydroxylamine derivativeof the formula (I-a). However, it is also possible to employ thereaction components in other ratios. Work-up is carried out by customarymethods. In general, the reaction mixture is mixed with water and theprecipitate is separated off and dried. The residue that remains can, ifappropriate, be freed by customary methods, such as chromatography orrecrystallization, from any impurities that may be present.

When carrying out the process (f) according to the invention, in general1 mol or else an excess of the phenyloxime derivative of the formula(VII) and from 1 to 5 mol of acid binder and 1 to 5 mol of a catalystare employed per mole of carboxamide derivative of the formula (IV).However, it is also possible to employ the reaction components in otherratios. Work-up is carried out by customary methods. In general, thereaction mixture is mixed with water and the precipitate is separatedoff and dried. The residue that remains can, if appropriate, be freed bycustomary methods, such as chromatography or recrystallization, from anyimpurities that may be present.

The substances according to the invention have potent microbicidalactivity and can be employed for controlling undesirable microorganisms,such as fungi and bacteria, in crop protection and in the protection ofmaterials.

Fungicides can be employed in crop protection for controllingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be employed in crop protection for controllingPseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceaeand Streptomycetaceae.

Some pathogens causing fungal and bacterial diseases which come underthe generic names listed above may be mentioned as examples, but not byway of limitation:

-   Xanthomonas species, such as, for example, Xanthomonas campestris    pv. oryzae;-   Pseudomonas species, such as, for example, Pseudomonas syringae pv.    lachrymans;-   Erwinia species, such as, for example, Erwinia amylovora;-   Pythium species, such as, for example, Pythium ultimum;-   Phytophthora species, such as, for example, Phytophthora infestans;-   Pseudoperonospora species, such as, for example, Pseudoperonospora    humuli or Pseudoperonospora cubensis;-   Plasmopara species, such as, for example, Plasmopara viticola;-   Bremia species, such as, for example, Bremia lactucae;-   Peronospora species, such as, for example, Peronospora pisi or P.    brassicae;-   Erysiphe species, such as, for example, Erysiphe graminis;-   Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;-   Podosphaera species, such as, for example, Podosphaera leucotricha;-   Venturia species, such as, for example, Venturia inaequalis;-   Pyrenophora species, such as, for example, Pyrenophora teres or P.    graminea (conidia form: Drechslera, syn: Helminthosporium);-   Cochliobolus species, such as, for example, Cochliobolus sativus    (conidia form: Drechslera, syn: Helminthosporium);-   Uromyces species, such as, for example, Uromyces appendiculatus;-   Puccinia species, such as, for example, Puccinia recondita;-   Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;-   Tilletia species, such as, for example, Tilletia caries;-   Ustilago species, such as, for example, Ustilago nuda or Ustilago    avenae;-   Pellicularia species, such as, for example, Pellicularia sasakii;-   Pyricularia species, such as, for example, Pyricularia oryzae;-   Fusarium species, such as, for example, Fusarium culmorunm;-   Botrytis species, such as, for example, Botrytis cinerea;-   Septoria species, such as, for example, Septoria nodorum;-   Leptosphaeria species, such as, for example, Leptosphaeria nodorum;-   Cercospora species, such as, for example, Cercospora canescens;-   Alternaria species, such as, for example, Alternaria brassicae; and-   Pseudocercosporella species, such as, for example,    Pseudocercosporella herpotrichoides.

The fact that the active compounds are well tolerated by plants at theconcentrations required for controlling plant diseases permits thetreatment of above-ground parts of plants, of propagation stock andseeds, and of the soil.

The active compounds according to the invention can be employedparticularly successfully for controlling diseases in viticulture andfruit and vegetable growing such as, for example, against Venturia,Botrytis, Sclerotinia, Rhizoctonia, Uncinula, Sphaerotheca, Podosphaera,Alternaria and Colletotrichum. Rice diseases, such as Pyricularia andPellicularia species, are likewise controlled with good results.

The active compounds according to the invention are also suitable forincreasing the yield of crops. In addition, they show reduced toxicityand are well tolerated by plants.

According to the invention, it is possible to treat all plants and partsof plants. By plants are understood here all plants and plantpopulations such as desired and undesired wild plants or crop plants(including naturally occurring crop plants). Crop plants can be plantswhich can be obtained by conventional breeding and optimization methodsor by biotechnological and genetic engineering methods or combinationsof these methods, including the transgenic plants and including theplant varieties which can or cannot be protected by varietal propertyrights. Parts of plants are to be understood as meaning all above-groundand below-ground parts and organs of plants, such as shoot, leaf, flowerand root, examples which may be mentioned being leaves, needles, stems,trunks, flowers, fruit-bodies, fruits and seeds and also roots, tubersand rhizomes. Parts of plants also include harvested plants andvegetative and generative propagation material, for example seedlings,tubers, rhizomes, cuttings and seeds.

In the protection of materials, the compounds according to the inventioncan be employed for protecting industrial materials against infectionwith, and destruction by, undesired microorganisms.

Industrial materials in the present context are understood as meaningnon-living materials which have been prepared for use in industry. Forexample, industrial materials which are intended to be protected byactive compounds according to the invention from microbial change ordestruction can be adhesives, sizes, paper and board, textiles, leather,wood, paints and plastic articles, cooling lubricants and othermaterials which can be infected with, or destroyed by, microorganisms.Parts of production plants, for example cooling-water circuits, whichmay be impaired by the proliferation of microorganisms may also bementioned within the scope of the materials to be protected. Industrialmaterials which may be mentioned within the scope of the presentinvention are preferably adhesives, sizes, paper and board, leather,wood, paints, cooling lubricants and heat-transfer liquids particularlypreferably wood.

Microorganisms capable of degrading or changing the industrial materialswhich may be mentioned are, for example, bacteria, fungi, yeasts, algaeand slime organisms. The active compounds according to the inventionpreferably act against fungi, in particular moulds, wood-discolouringand wood-destroying fungi (Basidiomycetes), and against slime organismsand algae.

Microorganisms of the following genera may be mentioned as examples:

-   Alternaria, such as Alternaria tenuis,-   Aspergillus, such as Aspergillus niger,-   Chaetomium, such as Chaetomium globosum,-   Coniophora, such as Coniophora puetana,-   Lentinus, such as Lentinus tigrinus,-   Penicillium, such as Penicillium glaucum,-   Polyporus, such as Polyporus versicolor,-   Aureobasidium, such as Aureobasidium pullulans,-   Sclerophoma, such as Sclerophoma pityophila,-   Trichoderma, such as Trichoderma viride,-   Escherichia, such as Escherichia coli,-   Pseudomonas, such as Pseudomonas aeruginosa, and-   Staphylococcus, such as Staphylococcus aureus.

Depending on their particular physical and/or chemical properties, theactive compounds can be converted to the customary formulations, such assolutions, emulsions, suspensions, powders, foams, pastes, granules,aerosols and microencapsuiations in polymeric substances and in coatingcompositions for seeds, and ULV cool and warm fogging formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurfactants, that is emulsifiers and/or dispersants, and/or foamformers. If the extender used is water, it is also possible to employ,for example, organic solvents as auxiliary solvents. Essentially,suitable liquid solvents are: aromatics such as xylene, toluene oralkylnaphthalenes, chlorinated aromatics or chlorinated aliphatichydrocarbons such as chlorobenzenes, chloroethylenes or methylenechloride, aliphatic hydrocarbons such as cyclohexane or paraffins, forexample petroleum fractions, alcohols such as butanol or glycol andtheir ethers and esters, ketones such as acetone, methyl ethyl ketone,methyl isobutyl ketone or cyclohexanone, strongly polar solvents such asdimethylformamide or dimethyl sulphoxide, or else water. Liquefiedgaseous extenders or carriers are to be understood as meaning liquidswhich are gaseous at standard temperature and under atmosphericpressure, for example aerosol propellants such as halogenatedhydrocarbons, or else butane, propane, nitrogen and carbon dioxide.Suitable solid carriers are: for example ground natural minerals such askaolins, clays, talc, chalk, quartz, attapulgite, montrnorillonite ordiatomaceous earth, and ground synthetic minerals such as finely dividedsilica, alumina and silicates. Suitable solid carriers for granules are:for example crushed and fractionated natural rocks such as calcite,marble, pumice, sepiolite and dolomite, or else synthetic granules ofinorganic and organic meals, and granules of organic material such assawdust, coconut shells, maize cobs and tobacco stalks. Suitableemulsifiers and/or foam fonners are: for example nonionic and anionicemulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylenefatty alcohol ethers, for example alkylaryl polyglycol ethers,alkylsulphonates, alkyl sulphates, arylsulphonates, or else proteinhydrolysates. Suitable dispersants are: for example lignin-sulphitewaste liquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins and syntheticphospholipids can be used in the formulations. Other possible additivesare mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs suchas alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs,and trace nutrients such as salts of iron, manganese, boron, copper,cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such orin their formulations, also in a mixture with known fungicides,bactericides, acaricides, nematicides or insecticides, to broaden, forexample, the activity spectrum or to prevent development of resistance.In many cases, synergistic effects are obtained, i.e. the activity ofthe mixture is greater than the activity of the individual components.

Examples of suitable mixing components are the following:

Fungicides:

-   aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine,    azaconazole, azoxystrobin,-   benalaxyl, benodanil, benomyl, benzamacril, benzamacril-isobutyl,    bialaphos, binapacryl, biphenyl, bitertanol, blasticidin-S,    bromuconazole, bupirimate, buthiobate,-   calcium polysulphide, capsimycin, captafol, captan, carbendazim,    carboxin, carvon, quinomethionate, chlobenthiazone, chlorfenazole,    chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon,    cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,-   debacarb, dichlorophen, diclobutrazole, diclofluanid, diclomezine,    dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph,    diniconazole, diniconazole-M, dinocap, diphenylamine, dipyrithione,    ditalimfos, dithianon, dodemorph, dodine, drazoxolon,-   edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,    famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram,    fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate,    fentin hydroxide, ferbam, ferimzone, fluazinam, flumetover,    fluoromide, fluquinconazole, flurprimidol, flusilazole,    flusulfamide, flutolanil, flutriafol, folpet, fosetyl-aluminium,    fosetyl-sodium, fthalide, fuberidazole, furalaxyl, furametpyr,    furcarbonil, furconazole, furconazolecis, furmecyclox,-   guazatine,-   hexachlorobenzene, hexaconazole, hymexazole, imazalil,    imibenconazole, iminoctadine, iminoctadine albesilate, iminoctadine    triacetate, iodocarb, ipconazole, iprobenfos (IBP), iprodione,    irumamycin, isoprothiolane, isovaledione,-   kasugamycin, kresoxim-methyl, copper preparations, such as: copper    hydroxide, copper naphthenate, copper oxychloride, copper sulphate,    copper oxide, oxine-copper and Bordeaux mixture,-   mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,    metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram,    metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,-   nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,    ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim,    oxyfenthiin, paclobutrazole, pefurazoate, penconazole, pencycuron,    phosdiphen, pimaricin, piperalin, polyoxin, polyoxorim, probenazole,    prochloraz, procymidone, propamocarb, propanosine-sodium,    propiconazole, propineb, pyrazophos, pyrifenox, pyrimethanil,    pyroquilon, pyroxyfur,-   quinconazole, quintozene (PCNB), quinoxyfen sulphur and sulphur    preparations,-   tebuconazole, tecloftalam, tecnazene, tetcyclacis, tetraconazole,    thiabendazole, thicyofen, thifluzamide, thiophanate-methyl, thiram,    tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol,    triazbutil, triazoxide, trichlamide, tricyclazole, tridemorph,    triflumizole, triforine, triticonazole,-   uniconazole,-   validamycin A, vinclozolin, viniconazole,-   zarilamide, zineb, ziram and also-   Dagger G,-   OK-8705,-   OK-8801,-   α-(1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,-   α-(2,4-dichlorophenyl)-β-fluoro-p-propyl-1H-1,2,4-triazole-1-ethanol,-   α-(2,4-dichlorophenyl)-β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,-   α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-l-ethanol,-   (5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,-   (E)-α-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,-   1-isopropyl    {2-methyl-1-[[[1-(4-methylphenyl)-ethyl]-amino]-carbonyl]-propyl}-carbamate,-   1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanone    O-(phenylmethyl)-oxime,-   1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,-   1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,-   1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,-   1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,-   1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,-   1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,    1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinole,-   2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide,-   2,2-dichloro-N-[-1-(4-chlorophenyl)-ethyl]-1-ethyl-3-methyl-cyclopropanecarboxamide,-   2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate,-   2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,-   2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,-   2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,-   2-[(1-methylethyl)-sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,-   2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-α-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,-   2-aminobutane,-   2-bromo-2-(bromomethyl)-pentanedinitrile,-   2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,-   2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,-   2-phenylphenol (OPP),-   3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,-   3,5-dichloro-N-[cyano[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,-   3-(1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,-   3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,-   4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,-   4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,-   8-(1,1-dimethylethyl)-N-ethyl-N-propyl-1,4-dioxaspiro[4.5]decane-2-methanamine,-   8-hydroxyquinoline sulphate,-   9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide,-   bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate,-   cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,-   cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholine-hydrochloride,-   ethyl [(4-chlorophenyl)-azo]-cyanoacetate,-   potassium hydrogen carbonate,-   methanetetrathiol sodium salt,-   methyl    1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,-   methyl N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,-   methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,-   N-(2,3-dichloro-4-hydroxyphenyl)-1-methyl-cyclohexanecarboxamide,-   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,-   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,-   N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,-   N-(4-cyclohexylphenyl)-1,4,5 ,6-tetrahydro-2-pyrimidineamine,-   N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidineamine,-   N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,-   N-(6-methoxy-3-pyridinyl)-cyclopropanecarboxamide,-   N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,-   N-[3-chloro-4,5-bis-(2-propinyloxy)-phenyl]-N-methoxy-methanimidamide,-   N-formyl-N-hydroxy-DL-alanine-sodium salt,-   O,O-diethyl    [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,-   O-methyl S-phenyl phenylpropylphosphoramidothioate,-   S-methyl 1,2,3-benzothiadiazole-7-carbothioate,-   spiro[2H]-1-benzopyrane-2,1′(3′H)-isobenzofuran]-3′-one,    Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dirnethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides:

-   abamectin, acephate, acetamiprid, acrinathrin, alanycarb, aldicarb,    aldoxycarb, alpha-cypermethrin, alphamethrin, amitraz, avermectin,    AZ 60541, azadirachtin, azamethiphos, azinphos A, azinphos M,    azocyclotin, Bacillus popilliae, Bacillus sphaericus, Bacillus    subtilis, Bacillus thuringiensis, baculoviruses, Beauveria bassiana,    Beauveria tenella, bendiocarb, benfuracarb, bensultap, benzoximate,    betacyfluthrin, bifenazate, bifenthrin, bioethanomethrin,    biopermethrin, BPMC, bromophos A, bufencarb, buprofezin,    butathiofos, butocarboxim, butylpyridaben,-   cadusafos, carbaryl, carbofuran, carbophenothion, carbosulfan,    cartap, chloethocarb, chlorethoxyfos, chlorfenapyr, chlorfenvinphos,    chlorfluazuron, chlormephos, chlorpyrifos, chlorpyrifos M,    chlovaphorthrin, cis-resmethrin, cispermethrin, clocythrin,    cloethocarb, clofentezine, cyanophos, cycloprene, cycloprothrin,    cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,    deltamethrin, demeton M, demeton S, demeton-S-methyl, diafenthiuron,    diazinon, dichlorvos, diflubenzuron, dimethoat, dimethylvinphos,    diofenolan, disulfoton, docusat-sodium, dofenapyn,-   elfusilanate, emamectin, empenthrin, endosulfan, Entomopfthora spp.,    esfenvalerate, ethiofencarb, ethion, ethoprophos, etofenprox,    etoxazole, etrimfos, fenamiphos, fenazaquin, fenbutatin oxide,    fenitrothion, fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin,    fenpyrad, fenpyrithrin, fenpyroximate, fenvalerate, fipronil,    fluazinam, fluazuron, flubrocythrinate, flucycloxuron,    flucythrinate, flufenoxuron, flutenzine, fluvalinate, fonophos,    fosmethilan, fosthiazate, fubfenprox, furathiocarb,-   granulosis viruses,-   halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox,    hydroprene,-   imidacloprid, isazofos, isofenphos, isoxathion, ivermectin,-   nuclear polyhedrosis viruses,-   lambda-cyhalothrin, lufenuron,-   malathion, mecarbam, metaldehyde, methamidophos, Metharhizium    anisopliae, Metharhizium flavoviride, methidathion, methiocarb,    methomyl, methoxyfenozide, metolcarb, metoxadiazone, mevinphos,    milbemectin, monocrotophos, naled, nitenpyram, nithiazine,    novaluron,-   omethoate, oxamyl, oxydemethon M,-   Paecilomyces fumosoroseus, parathion A, parathion M, permethrin,    phenthoate, phorat, phosalone, phosmet, phosphamidon, phoxim,    pirimicarb, pirimiphos A, pirimiphos M, profenofos, promecarb,    propoxur, prothiofos, prothoat, pymetrozine, pyraclofos,    pyresmethrin, pyrethrum, pyridaben, pyridathion, pyrimidifen,-   pyriproxyfen,-   quinalphos,-   ribavirin,-   salithion, sebufos, silafluofen, spinosad, sulfotep, sulprofos,-   tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos,    teflubenzuron, tefluthrin, temephos, temivinphos, terbufos,    tetrachlorvinphos, theta-cypermethrin, thiamethoxam, thiapronil,    thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox,    thuringiensin, tralocythrin, tralomethrin, triarathene, triazamate,    triazophos, triazuron, trichlophenidine, trichlorfon, triflumuron,    trimethacarb, vamidothion, vaniliprole, Verticillium lecanii,-   YI 5302-   zeta-cypermethrin, zolaprofos-   (1R-cis)-[5-(phenylmethyl)-3-furanyl]-methyl-3-[(dihydro-2-oxo-3(2H)-furanylidene)-methyl]-2,2-dimethylcyclopropanecarboxylate,-   (3-phenoxyphenyl)-methyl-2,2,3,3-tetramethylcyclopropanecarboxylate,-   1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine,-   2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]-4,5-dihydro-oxazole,-   2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione,-   2-chloro-N-[[[4-(1-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide,-   2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide,-   3-methylphenyl propylcarbamate-   4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxy-benzene,-   4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone,-   4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone,-   4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone,-   Bacillus thuringiensis strain EG-2348,-   [2-benzoyl-1-(1,1-dimethylethyl)-hydrazinobenzoic acid,-   2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-yl    butanoate,-   [3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide,    dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde,    ethyl    [2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate,-   N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine,-   N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,-   N-[(2-chloro-5-thiazolyl)methyl]-N′-methyl-N′-nitro-guanidine,-   N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,-   N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide,-   O,O-diethyl    [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate.

A mixture with other known active compounds, such as herbicides, or withfertilizers and growth regulators, is also possible.

In addition, the compounds of the formula (I) according to the inventionalso have very good antimycotic activity. They have a very broadantirnycotic activity spectrum in particular against dermatophytes andyeasts, moulds and diphasic fungi,

for example against Candida species, such as Candida albicans, Candidaglabrata, Epidermophyton species, such as Epidermophyton floccosum,Aspergillus species, such as Aspergillus niger and Aspergillusfumigatus, Trichophyton species, such as Trichophyton mentagrophytes,Microsporon species such as Microsporon canis and audouinii.

The list of these fungi by no means limits the mycotic spectrum covered,but is only for illustration.

The active compounds can be used as such, in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, suspensions, wettable powders, pastes, soluble powders, dustsand granules. Application is carried out in a customary manner, forexample by watering, spraying, atomizing, broadcasting, dusting,foaming, spreading, etc. It is furthermore possible to apply the activecompounds by the ultra-low volume method, or to inject the activecompound preparation or the active compound itself into the soil. It isalso possible to treat the seeds of the plants.

When using the active compounds according to the invention asfungicides, the application rates can be varied within a relatively widerange, depending on the kind of application. For the treatment of partsof plants, the active compound application rates are generally between0.1 and 10,000 g/ha, preferably between 10 and 1000 g/ha. For seeddressing, the active compound application rates are generally between0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 gper kilogram of seed. For the treatment of the soil, the active compoundapplication rates are generally between 0.1 and 10,000 g/ha, preferablybetween 1 and 5000 g/ha.

The compositions used for protecting industrial materials comprise theactive compounds generally in an amount of from 1 to 95%, preferablyfrom 10 to 75%.

The use concentrations of the active compounds according to theinvention depend on the nature and occurrence of the microorganisms tobe controlled and on the composition of the material to be protected.The optimum amount. employed can be determined by a series of tests. Ingeneral, the use concentrations are in the range from 0.001 to 5% byweight, preferably from 0.05 to 1.0% by weight, based on the material tobe protected.

The activity and the activity spectrum of the active compounds to beused according to the invention in material protection, or thecompositions, concentrates or quite generally formulations preparabletherefrom can be increased by adding, if appropriate, furtherantimicrobially active compounds, fungicides, bactericides, herbicides,insecticides or other active compounds for widening the activityspectrum or obtaining particular effects, such as, for example,additional protection against insects. These mixtures may have a wideractivity spectrum than the compounds according to the invention.

The preparation and the use of the active compounds according to theinvention is shown in the examples below.

PRREPARETION EXAMPLES Example 1

Process (a):

At room temperature, a solution of 1.3 g (0.0057 mol) of2′-amino-1,1′-biphenyl-4-carbaldehyde O-methyloximine in 20 ml oftoluene is admixed with 0.57 g (0.0057 mol) of triethylamine. At roomtemperature, a solution of 1.0 g (0.0057 mol) of5-fluoro-1,3-dimethyl-1H-pyrazole-4-carbonyl chloride in 5 ml of tolueneis added dropwise with stirring to this mixture. After the addition hasended, the reaction mixture is heated to 50° C. and stirred at thistemperature for a further 2 h. For work-up, the reaction mixture iscooled to room temperature, mixed with another 25 ml of toluene andwashed with water. The organic phase is separated off, dried over sodiumsulphate, filtered and concentrated under reduced pressure. The residuethat remains is recrystallized from diisopropyl ether. In this manner,1.45 g (69.4% of theory) of5-fluoro-N-{4′-[(methoxyimino)methyl]-1,1′-biphenyl-2-yl}-1,3-dimethyl-1H-pyrazole-4-carboxamideare obtained as colourless crystals of melting point 114 to 116° C.

Example 2

Process (b):

At room temperature, a mixture of 0.35 g (0.001 mol) ofN-(2-bromo-4,6-difluorophenyl)-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide,0.06 g (0.00005 mol) of tetrakis-(triphenylphosphine)-palladium, 0.32 g(0.0018 mol) of 4-[(methoxyimino)methyl]phenylboronic acid and 10 ml of1,2-dimethoxyethane is admixed with a solution of 0.5 g (0.0047 mol) ofsodium carbonate in 3 ml of water. The reaction mixture is then heatedto reflux temperature and kept at this temperature for 15 h. Forwork-up, the reaction mixture is stirred into 200 ml of water. Theresulting precipitate is filtered off with suction and dried. Theresidue that remains is chromatographed on silica gel using the mobilephase cyclohexane : ethyl acetate=1:1. Concentration of the eluate gives0.20 g (48% of theory) ofN-{3,5-difluoro-4′-[(methoxyimino)methyl]-1,1′-biphenyl-2-yl}-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamidein the form of a solid of melting point 164 to 167° C.

Example 3

Process (c):

At room temperature, 1.28 g (12 mmol) of sodium carbonate, dissolved in6 ml of water, are added to a mixture of 0.71 g (2 mmol) of5-fluoro-1,3-dimethyl-N-[2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1H-pyrazole-4-carboxamide,1.39 g (6 mmol) of 4-bromo-2-fluorobenzaldehyde O-methyloxime, 0.03 g(0.05 mmol) of PdCI₂(dppf) and 40 ml of dimethyl sulphoxide. Thereaction mixture is stirred at 80° C. for 15 hours.

For work-up, the reaction mixture is stirred into 400 ml of water andthe precipitate is filtered off with suction and dried. The crudeproduct is then purified by silica gel column chromatography using themobile phase cyclohexane: ethyl acetate=1:1. Concentration gives 0.11 g(14% of theory) of 5-fluoro-N-{3′-fluoro-4′-[(methoxyimino)methyl]-1,1′-biphenyl-2-yl}-1,3-dimethyl-1H-pyrazole-4-carbox-amide as crystals ofmelting point 158 to 161° C.

Example 4

Process (d):

A mixture of 1.0 g (0.0028 mol) ofN-(4′-acetyl-1,1′-biphenyl-2-yl)-5-fluoro-1,3-dimethyl-1H-pyrazole-4-carboxamide,0.30 g (0.0036 mol) of O-methyl-hydroxylamine hydrochloride, 0.30 g(0.0036 mol) of sodium acetate and 6 ml of methanol is stirred at roomtemperature for 12 h. For work-up, the reaction mixture is stirred intowater and the resulting precipitate is filtered off with suction, washedwith water and then with a little diisopropyl ether and dried. Thisgives 0.91 g (85.4% of theory) of5-fluoro-N-[4′-(N-methoxyethaneimidoyl)-1,1′-biphenyl-2-yl]-1,3-dimethyl-1H-pyrazole-4-carboxamideof melting point 153° C.

¹H-NMR spectrum (DMSO/TMS): δ=3.60 ppm.

Preparation of Starting Materials

Process (g):

At room temperature, a mixture of 2.9 g (0.017 mol) of 2-bromoaniline,0.68 g of tetrakis-(triphenylphosphine)-palladium, 5.5 g (0.031 mol) of4-[(methoxyimino)methyl]phenylboronic acid and 40 ml of1,2-dimethoxyethane is admixed with a solution of 8.2 g (0.077 mol) ofsodium carbonate in 35 ml of water. The reaction mixture is then heatedto reflux temperature and boiled for 12 h. For work-up, the mixture iscooled to room temperature and extracted with diethyl ether. The organicphase is separated off and admixed with water. The organic phase isagain separated off, dried over sodium sulphate and finally concentratedunder reduced pressure. The residue that remains is chromatographed onsilica gel using the mobile phase cyclohexane:ethyl acetate=3:1. Theeluate is concentrated, giving 3.8 g (98.8% of theory based on2-bromoaniline) of 2′-amino-1,1′-biphenyl-4-carbaldehyde O-methyloximein the form of an oil.

¹H-NMR spectrum (DMSO/TMS): δ=3.90 (3H) ppm.

Process (i):

A mixture of 5.0 g (0.033 mol) of 4-formylphenylboronic acid, 3.4 g(0.041 mol) of O-methylhydroxylamine hydrochloride, 3.4 g (0.041 mol) ofsodium acetate, 40 ml of methanol and 10 ml of water is stirred at roomtemperature for 12 h. For work-up, the reaction mixture is stirred withwater and the resulting precipitate is filtered off with suction, washedwith water and dried at 50° C. under reduced pressure. This gives 5.56 g(93.1% of theory) of 4-[(methoxyimino)methyl]phenylboronic acid ascolourless crystals of melting point 199-200° C.

Process (j):

0.55 g (4 mmol) of potassium carbonate and 0.30 g (0.0017 mol) of5-fluoro-1,3-dimethyl-1H-pyrazole-4-carbonyl chloride are, at roomtemperature, added to a mixture of 0.39 g (1.5 mmol) of2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline hydrochloride and20 ml of acetonitrile. The reaction mixture is stirred at roomtemperature for 20 h.

For work-up, the reaction mixture is stirred into 150 ml of water andextracted with ethyl acetate, and the extract is dried over sodiumsulphate. The organic phase is concentrated under reduced pressure andthe solid residue is stirred with diisopropyl ether. This gives 0.25 g(46% of theory) of5-fluoro-1,3-dimethyl-N-[2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-1H-pyrazole-4-carboxamidein the form of crystals of melting point 100-103° C.

The biphenylcarboxamides of the formula (I) listed in the table beloware also prepared by the methods described above. TABLE 1 Ex. PhysicalNo. Compound constant 5

m.p. 122-125° C. 6

m.p. 144-145° C. 7

logP 3.20^(a)) 8

logP 3.39^(a)) 9

logP 2.51^(a)) 10

logP 3.26^(a)) 11

logP 3.05^(a)) 12

logP 1.75^(a)) 13

logP 4.02^(a)) 14

logP 3.68^(b)) 15

logP 1.81^(a)) 16

logP 1.72^(a)) 17

logP 1.89^(a)) 18

logP 1.69^(a)) 19

logP 1.60^(a)) 20

m.p. 115-117° C. 21

m.p. 124-126° C. 22

m.p. 115-117° C. 23

m.p. 115-117° C. 24

m.p. 102-104° C. 25

logP 3.38^(a)) 26

logP 3.40^(a)) 27

logP 3.15^(a)) 28

logP 3.67^(a)) 29

logP 3.39^(a)) 30

logP 3.27^(a)) 31

logP 3.34^(a)) 32

logP 3.10^(a)) 33

logP 3.79^(a)) 34

logP 3.74^(a)) 35

logP 3.11^(a)) 36

logP 3.48^(a)) 37

logP 3.01^(a)) 38

logP 3.58^(a)) 39

logP 3.91^(a)) 40

logP 4.63^(a)) 41

logP 3.89^(a)) 42

logP 4.09^(a)) 43

logP 4.06^(a)) 44

logP 4.63^(a)) 45

m.p. 147-149° C. 46

logP 3.47^(a)) 47

logP 3.30^(a)) 48

logP 3.25^(a)) 49

50

logP 3.89^(a)) 51

logP 4.67^(a)) 52

53

logP 2.24^(a)) 54

m.p. 97-99° C. 55

logP 4.33^(a))

The logP values given in the Preparation Examples and Tables above weredetermined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC(High Performance Liquid Chromatography) on a reversed-phase column (C18). Temperature: 43° C.

In the acidic range, the determination was carried out at pH 2.3 usingthe mobile phases 0.1% aqueous phosphoric acid and acetonitrile; lineargradient from 10% acetonitrile to 90% acetonitrile (marked a) in theTable).

In the neutral range, the determination was carried out at pH 7.5 usingthe mobile phases 0.01 molar aqueous phosphate buffer solution andacetonitrile; linear gradient from 10% acetonitrile to 90% acetonitrile(marked ^(b)) in the Table).

Calibration was carried out using unbranched alkan-2-ones (having 3 to16 carbon atoms) with known logP values (determination of the logPvalues by the retention times using linear interpolation between twosuccessive alkanones).

The lambda max values were determined in the maxima of thechromatographic signals using the UV spectra from 200 nm to 400 nm.

USE EXAMPLES Example A

Podosphaera test (apple)/protective Solvents: 24.5 parts by weight ofacetone 24.5 parts by weight of dimethylacetamide Emulsifier:  1.0 partby weight of alkyl-aryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of the apple mildew pathogen Podosphaera leucotricha.The plants are then placed in a greenhouse at approximately 23° C. and arelative atmospheric humidity of approximately 70%.

Evaluation is carried out 10 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, for example, the following compounds according to theinvention of the Preparation Examples exhibit an activity which issuperior to that of the prior art: TABLE A Podosphaera test(apple)/protective Application rate of active compound Active compoundin g/ha % efficacy (I-1) 

100 100 (I-8) 

100 98 (I-11)

100 100 (I-20)

100 95 (I-22)

100 99 (I-23)

100 100 (I-26)

100 100 (I-29)

100 94 (I-37)

100 100 (I-39)

100 100 (I-46)

100 100 (I-47)

100 100 (I-50)

100 100

Example B

Sphaerotheca test (cucumber)/protective Solvents: 24.5 parts by weightof acetone 24.5 parts by weight of dimethylacetamide Emulsifier:  1.0part by weight of alkyl-aryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of Sphaerotheca fuiginea. The plants are then placed ina greenhouse at approximately 23° C. and a relative atmospheric humidityof approximately 70%.

Evaluation is carried out 10 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, for example, the following compounds according to theinvention of the Preparation Examples exhibit an activity which issuperior to that of the prior art: TABLE B Sphaerotheca test(cucumber)/protective Application rate of active Active compoundcompound in g/ha % efficacy (I-1) 

100 100 (I-11)

100 93 (I-20)

100 77 (I-22)

100 95 (I-23)

100 95 (I-26)

100 95 (I-29)

100 83 (I-37)

100 77 (I-39)

100 97 (I-46)

100 100 (I-47)

100 100 (I-50)

100 100

Example C

Venturia test (apple)/protective Solvents: 24.5 parts by weight ofacetone 24.5 parts by weight of dimethylacetamide Emulsifier:  1.0 partby weight of alkyl-aryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousconidia suspension of the apple scab pathogen Venturia inaequalis andthen remain in an incubation cabin at approximately 20° C. and 100%relative atmospheric humidity for 1 day.

The plants are then placed in a greenhouse at approximately 21° C. and arelative atmospheric humidity of approximately 90%.

Evaluation is carried out 12 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, for example, the following compounds according to theinvention of the Preparation Examples exhibit an activity which issuperior to that of the prior art: TABLE C Venturia test(apple)/protective Application rate of active compound in Activecompound g/ha % efficacy (I-1) 

100 100 (I-8) 

100 99 (I-11)

100 100 (I-20)

100 100 (I-22)

100 100 (I-23)

100 100 (I-26)

100 100 (I-29)

100 100 (I-37)

100 100 (I-39)

100 100 (I-46)

100 100 (I-47)

100 100 (I-50)

100 100

Example D

Puccinia test (wheat)/protective Solvent:  25 parts by weight ofN,N-dimethylacetamide Emulsifier: 0.6 part by weight of alkylarylpolyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound at the stated application rate. After thespray coating has dried on, the plants are sprayed with a conidiasuspension of Puccinia recondita. The plants remain in an incubationcabin at 20° C. and 100% relative atmospheric humidity for 48 hours.

The plants are then placed in a greenhouse at a temperature ofapproximately 20° C. and a relative atmospheric humidity of 80% topromote the development of rust pustules.

Evaluation is carried out 10 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, for example, the following compounds according to theinvention of the Preparation Examples exhibit an activity which issuperior to that of the prior art: TABLE D Puccinia test(wheat)/protective Application rate of active compound Active compoundin g/ha % efficacy (I-1) 

250 100 (I-3) 

250 100 (I-9) 

250 100 (I-20)

250 100 (I-22)

250 100 (I-26)

250 100

Example E

Alternaria test (tomato)/protective Solvent: 49 parts by weight ofN,N-dimethylformamide Emulsifier:  1 part by weight of alkylarylpolyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young tomato plants are sprayed withthe preparation of active compound at the stated application rate. 1 dayafter the treatment, the plants are inoculated with a spore suspensionof Alternaria solani and then remain at 100% rel. humidity and 20° C.for 24 h. The plants then remain at 96% rel. atmospheric humidity and atemperature of 20° C.

Evaluation is carried out 7 days after the inoculation. 0% means anefficacy which corresponds to that of the control, whereas an efficacyof 100% means that no infection is observed.

In this test, for example, the following compounds according to theinvention of the Preparation Examples exhibit an activity which issuperior to that of the prior art: TABLE E Altemaria test(tomato)/protective Application rate of active compound Active compoundin g/ha % efficacy (I-1)

750 95 (I-2)

750 90 (I-4)

750 90 (I-5)

750 90 (I-7)

750 100

Example F Inhibition Test on Giant Colonies of Basidiomycetes

Mycelium sections were removed from colonies of Gloeophyllum trabeum,Coniophora puteana, Poria placenta, Lentinus tigrinus and Coriolusversicolor and incubated on an agar medium containing malt extractpeptone at 26° C. The inhibition of hyphal growth onactive-compound-containing media was compared with the longitudinalgrowth on media without an addition of active compound and rated aspercent inhibition.

In this test, for example, the following compounds according to theinvention of the Preparation Examples exhibit good activity: TABLE FInhibition test on giant colonies of Basidiomycetes Application rate ofactive compound Active compound in ppm % efficacy (I-1)

6 100 (I-3)

6 100 (I-4)

6 100 (I-9)

6 100

1-21. (canceled)
 22. A pyrazolylbiphenylcarboxamide of the formula (I)

wherein R¹ represents benzyl or pyridylmethyl, R² represents hydrogen orC₁-C₆-alkyl, X represents halogen, nitro, cyano, hydroxyl, carboxyl,C₁-C₈-alkyl, C₁-C₆-halogenoalkyl having 1 to 5 halogen atoms,C₁-C₈-alkoxy, C₁-C₆-halogenoalkoxy having 1 to 5 halogen atoms,C₁-C₈-alkylthio, C₁-C₆-halogenoalkylthio having 1 to 5 halogen atoms,C₂-C₈-alkenyloxy, C₂-C₈-alkinyloxy, C₃-C₈-cycloalkyl,C₁-C₈-alkoxycarbonyl or represents —C(R²)═N—OR¹, m represents integersfrom 0 to 3, where X represents identical or different radicals if mrepresents 2 or 3, Y represents halogen, nitro, cyano, hydroxyl,carboxyl, C₁-C₈-alkyl, C₁-C₆-halogenoalkyl having 1 to 5 halogen atoms,C₁-C₈-alkoxy, C₁-C₆-halogenoalkoxy having 1 to 5 halogen atoms,C₁-C₈-alkylthio, C₁-C₆-halogenoalkylthio having 1 to 5 halogen atoms,C₂-C₈-alkenyloxy, C₂-C₈-alkinyloxy, C₃-C₈-cycloalkyl,C₁-C₈-alkoxycarbonyl or C₁-C₆-alkox-imino-C₁-C₆-alkyl and n representsintegers from 0 to 4, where Y represents identical or different radicalsif n represents 2, 3 or
 4. 23. The pyrazolylbiphenylcarboxamide of theformula (I) according to claim 22 wherein R¹ represents benzyl orpyridylmethyl, R² represents hydrogen or C₁-C₄-alkyl, X representsfluorine, chlorine, bromine, nitro, cyano, hydroxyl, carboxyl,C₁-C₆-alkyl, C₁-C₂-halogenoalkyl having 1 to 5 fluorine, chlorine and/orbromine atoms, C₁-C₆-alkoxy, C₁-C₂-halogenoalkoxy having 1 to 5fluorine, chlorine and/or bromine atoms, C₁-C₆-alkylthio,C₁-C₂-halogenoalkylthio having 1 to 5 fluorine, chlorine and/or bromineatoms, C₂-C₆-alkenyloxy, C₂-C₆-alkinyloxy, C₃-C₇-cycloalkyl,C₁-C₄-alkoxycarbonyl or represents —C(R²)═N—OR¹, m represents integersfrom 0 to 3, where X represents identical or different radicals if mrepresents 2 or 3, Y represents fluorine, chlorine, bromine, nitro,cyano, hydroxyl, carboxyl, C₁-C₆-alkyl, C₁-C₂-halogenoalkyl having 1 to5 fluorine, chlorine and/or bromine atoms, C₁-C₆-alkoxy,C₁-C₂-halogenoalkoxy having 1 to 5 fluorine, chlorine and/or bromineatoms, C₁-C₆-alkylthio, C₁-C₂-halogenoalkylthio having 1 to 5 fluorine,chlorine and/or bromine atoms, C₂-C₆-alkenyloxy, C₂-C₆-alkinyloxy,C₃-C₇-cycloalkyl, C₁-C₄-alkoxycarbonyl or C₁-C₄-alkoximino-C₁-C₄-alkyl,n represents integers from 0 to 3, where Y represents identical ordifferent radicals if n represents 2 or
 3. 24. Thepyrazolylbiphenylcarboxamide of the formula (I) according to claim 22wherein R¹ represents benzyl, 2-pyridylmethyl, 3-pyridylmethyl or4-pyridylmethyl, R² represents hydrogen, methyl, ethyl, n-propyl,i-propyl or n-butyl, X represents fluorine, chlorine, bromine, nitro,cyano, hydroxyl, carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl,sec-butyl, i-butyl, tert-butyl, trichloromethyl, trifluoromethyl,difluoromethyl, difluorochloromethyl, methoxy, ethoxy, difluoromethoxy,trifluoromethoxy, methylthio, trifluoromethylthio,difluorochloromethylthio, allyloxy, propargyloxy, cyclopropyl,cyclopentyl, cyclohexyl, cycloheptyl, methoxycarbonyl, ethoxycarbonyl orrepresents —C(R²)═N—OR¹, m represents integers from 0 to 2, where Xrepresents identical or different radicals if m represents 2, Yrepresents fluorine, chlorine, bromine, nitro, cyano, hydroxyl,carboxyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl,i-butyl, tert-butyl, trichloromethyl, trifluoromethyl, difluoromethyl,difluorochloromethyl, methoxy, ethoxy, difluoromethoxy,trifluoromethoxy, methylthio, trifluoromethylthio,difluorochloromethylthio, allyloxy, propargyloxy, cyclopropyl,cyclopentyl, cyclohexyl, cycloheptyl, methoxycarbonyl, ethoxycarbonyl ormethoximinomethyl, n represents integers from 0 to 2, where Y representsidentical or different radicals if n represents
 2. 25. A process forpreparing a pyrazolylbiphenylcarboxamide of the formula (I) according toclaim 22, comprising a) reacting a carboxylic acid derivative of theformula (II)

wherein G represents halogen, hydroxyl or C₁-C₆-alkoxy, with an anilinederivative of the formula (III)

wherein R¹, R², X, m, Y and n are each as defined in claim 22,optionally in the presence of a catalyst, optionally in the presence ofan acid binder and optionally in the presence of a diluent, or b)reacting a carboxamide derivative of the formula (IV)

wherein X and m are each as defined in claim 22, with a boronic acidderivative of the formula (V)

wherein R¹, R², Y and n are each as defined in claim 22 and G¹ and G²each represent hydrogen or together represent tetramethylethylene,optionally in the presence of a catalyst, optionally in the presence ofan acid binder and optionally in the presence of a diluent, or c)reacting a carboxamide-boronic acid derivative of the formula (VI)

wherein X and m are each as defined in claim 22 and G¹ and G² eachrepresent hydrogen or together represent tetramethylethylene, with aphenyloxime derivative of the formula (VIl)

wherein R¹, R², Y and n are each as defined in claim 22, optionally inthe presence of a catalyst, optionally in the presence of an acid binderand optionally in the presence of a diluent, or d) reacting abiphenylacyl derivative of the formula (VIII)

wherein R², X, m, Y and n are each as defined in claim 22, with analkoxamine of the formula (IX)R¹—O—NH₂×HCl  (IX) wherein R¹ is as defined in claim 22, optionally inthe presence of an acid binder and optionally in the presence of adiluent, or e) reacting a hydroxylamine derivative of the formula (I-a)

wherein R², X, m, Y and n are each as defined in claim 22, with acompound of the formula (X)R³-E  (X) wherein R³ represents C₁-C₆-alkyl and E represents chlorine,bromine, iodine, methanesulphonyl or p-toluenesulphonyl, or R³ and Etogether represent di-C₁-C₆-alkyl sulphate, optionally in the presenceof an acid binder and optionally in the presence of a diluent, or f)reacting a carboxamide derivative of the formula (IV)

wherein X and m are each as defined in claim 22, with a phenyloximederivative of the formula (VII)

wherein R¹, R², Y and n are each as defined in claim 22, in the presenceof a palladium or platinum catalyst and in the presence of4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bis-1,3,2-dioxaborolane, optionallyin the presence of an acid binder and optionally in the presence of adiluent.
 26. A pyrazolylbiphenylcarboxamide of the formula (I-b)

wherein R¹, R², X, m, Y and n are each as defined in claim
 22. 27. Apyrazolylbiphenylcarboxamide of the formula (I-c)

wherein R¹, R², X, m, Y and n are each as defined in claim
 22. 28. Apyrazolylbiphenylcarboxamide of the formula (I-d)

wherein R¹, R², X, m, Y and n are each as defined in claim
 22. 29. Ananiline derivative of the formula (III)

wherein R¹ represents hydrogen, C₁-C₆-alkyl, C₁-C₆-halogenoalkyl, benzylor pyridylmethyl, and R², X, m, Y and n are each as defined in claim 22.30. A process for preparing an aniline derivative of the formula (III)according to claim 29, comprising g) reacting a 2-halogenoanilinederivative of the formula (XI)

wherein X and m are each as defined in claim 22 and Hal representshalogen, with a boronic acid derivative of the formula (V)

wherein R¹ represents hydrogen, C₁-C₆-alkyl, C₁-C₆-halogenoalkyl, benzylor pyridylmethyl, and R², Y and n are each as defined in claim 22 and G¹and G² each represent hydrogen or together representtetramethylethylene, optionally in the presence of an acid binder, andoptionally in the presence of an inert organic diluent, and optionallyin the presence of a catalyst, or h) reacting an anilineboronic acid ofthe formula (XII)

wherein X and m are each as defined in claim 22 and G¹ and G² eachrepresent hydrogen or together represent tetramethylethylene, with aphenyloxime derivative of the formula (VII)

wherein R¹ represents hydrogen, C₁-C₆-alkyl, C₁-C₆-halogenoalkyl, benzylor pyridylmethyl, and R², Y and n are each as defined in claim 22,optionally in the presence of an acid binder, and optionally in thepresence of an inert organic diluent, and optionally in the presence ofa catalyst.
 31. A boronic acid derivative of the formula (V)

wherein R¹ represents hydrogen, C₁-C₆-alkyl, C₁-C₆-halogenoalkyl, benzylor pyridylmethyl, and R², Y and n are each as defined in claim 22 and G¹and G² each represent hydrogen or together representtetramethylethylene.
 32. A process for preparing a boronic acidderivative of the formula (V) according to claim 31, comprising i)reacting a phenylboronic acid of the formula (XIII)

wherein R², Y and n are each as defined in claim 22 and G¹ and G² eachrepresent hydrogen or together represent tetramethylethylene, with analkoxamine of the formula (IX)R¹—O—NH₂×HCl  (IX) wherein R¹ represents hydrogen, C₁-C₆-alkyl,C₁-C₆-halogenoalkyl, benzyl or pyridylmethyl, and optionally in thepresence of an acid binder, and optionally in the presence of an inertorganic diluent, and optionally in the presence of a catalyst.
 33. Acarboxamide-boronic acid derivative of the formula (VI)

wherein X and m are each as defined in claim 22 and G¹ and G² eachrepresent hydrogen or together represent tetramethylethylene.
 34. Aprocess for preparing a carboxamide-boronic acid derivative of theformula (VI) according to claim 33, comprising j) reacting a carboxylicacid derivative of the formula (II)

wherein G is as defined in claim 22, with an anilineboronic acid of theformula (XII)

wherein X and m are each as defined in claim 22 and G¹ and G² eachrepresent hydrogen or together represent tetramethylethylene, optionallyin the presence of an acid binder, and optionally in the presence of aninert organic diluent, and optionally in the presence of a catalyst. 35.A biphenylacyl derivative of the formula (VIII)

wherein R², X, m, Y and n are each as defined in claim
 22. 36. A processfor preparing a biphenylacyl derivative of the formula (VIII) accordingto claim 35, comprising k) reacting a carboxylic acid derivative of theformula (II)

wherein G is as defined in claim 22, with a 2-benzaldehyde-anilinederivative of the formula (XIV)

wherein R², X, m, Y and n are each as defined in claim 22, optionally inthe presence of an acid binder, and optionally in the presence of aninert organic diluent.
 37. A 2-benzaldehyde-aniline derivative of theformula (XIV)

wherein R², X, m, Y and n are each as defined in claim
 22. 38. A processfor preparing a 2-benzaldehyde-aniline derivative of the formula (XIV)according to claim 37, comprising l) reacting an aniline derivative ofthe formula (XI)

wherein X and m are each as defined in claim 22 and Hal representshalogen, with a phenylboronic acid derivative of the formula (XIII)

wherein R², Y and n are each as defined in claim 22 and G¹ and G² eachrepresent hydrogen or together represent tetramethylethylene, optionallyin the presence of an acid binder, and optionally in the presence of aninert organic diluent.
 39. A composition for controlling undesirablemicroorganisms, comprising at least one pyrazolylbiphenylcarboxamide ofthe formula (I) according to claim 22, and one or more extenders and/orsurfactants.
 40. A method for controlling undesirable microorganisms,comprising applying an effective amount of apyrazolylbiphenylcarboxamide of the formula (I) according to claim 22 tothe microorganisms and/or their habitat.
 41. A process for preparing acomposition for controlling undesirable microorganisms, comprisingmixing a pyrazolylbiphenylcarboxamide of the formula (I) according toclaim 22 with one or more extenders and/or surfactants.